十氢化萘低温燃烧反应的动力学机理

doi:10.7503/cjcu20180160

摘要/Abstract

摘要：

采用量子化学方法研究了十氢化萘低温燃烧的动力学机理, 获得了脱氢反应、自由基加氧反应及1,5氢迁移反应等反应的动力学参数, 并在CBS-QB3水平下获得了相关物种的热力学参数, 通过过渡态理论计算获得了具有紧致过渡态反应的高压极限速率常数, 而无能垒反应的速率常数则由变分过渡态理论得到. 基于此机理分析了十氢化萘低温反应的动力学规律和热力学机制. 相比于链烷烃和单环烷烃, 十氢化萘自由基加氧反应的速率常数随温度变化较快, 1,5-氢迁移反应的能垒较高, 揭示了物质结构对反应动力学的影响. 热力学平衡常数分析结果表明, 在低温下十氢化萘自由基加氧反应起主导作用. 通过拟合获得了所有反应Arrhenius形式的速率常数, 这些参数可用于双环烷烃低温燃烧机理的构建和优化.

关键词: 十氢化萘, 低温机理, 速率常数, 燃烧反应, 动力学机理

Abstract:

The kinetic mechanism of low-temperature decalin combustion was studied, including reaction types such as dehydrogenation reaction, radical oxygenation reaction and 1,5 H-shift reaction. The thermodynamic parameters of species were obtained at CBS-QB3 level. The high pressure limit rate constants for reactions with transition state were obtained by transition state theory calculations, while the rate constants for barrierless reactions were obtained by variational transition state theory. Based on this mechanism, the kinetic and thermodynamic behavior of decalin oxidation reactions at low temperature were analyzed. Compared with the corresponding results from linear alkanes and monocycloalkane, the rate constants of O₂-addition to decalin radical change more fast with temperature and the energy barriers of 1,5 H-shift reactions are higher, which reveal the influence of reactant structure on kinetics. The analysis result of thermodynamic equilibrium constants showed that the O₂-addition reaction to decalin radical plays a leading role at low temperature. The rate constants of Arrhenius form for all reactions were fitted and these parameters can be used in the construction and optimization of low temperature combustion mechanism of bicycloalkane.

Key words: Decalin, Low-temperature mechanism, Rate constant, Combustion reaction, Kinetic mechanism

中图分类号:

O641

TrendMD:

李颖丽, 王静波, 李象远. 十氢化萘低温燃烧反应的动力学机理. 高等学校化学学报, 2018, 39(6): 1212.

LI Yingli, WANG Jingbo, LI Xiangyuan. Kinetic Mechanism Study on Low Temperature for Decalin Combustion^†. Chem. J. Chinese Universities, 2018, 39(6): 1212.

图/表 12

Fig.1 Negative temperature coefficient effect of low temperature ignition delay(A), the disproportionation reaction of radical oxidation(B) and the barrierless reaction for O2 addition(C)

Fig.2 Structure and atomic sites of decalin

Fig.3 Low temperature oxidation reactions of decalin starting from C—H bond breaking at the α position(A) and β position(B)Species designation is also given.

Fig.4 Potential energy surface for the low temperature oxidation reactions starting from the α position and β position of decalin

Fig.5 Potential energy profile at the UB3LYP/CBSB7 level for the barrierless reactions of R=R1+H(A), R1+O2=R1-P1-OO(B) and R1-P2-OO+O2=R1-P3O4(C)

Table 1 High-pressure limit rate parameters for low temperature oxidation reactions of decalin in the temperature range of 500—1500 K*

Number of reaction	Reaction	lgA^*	E_a/(kJ·mol^-1)
r1	R=R1+H	14.91	300.33
r2	R1+O₂=R1-P1-OO	-0.62	63.79
r3	R1-P1-OO→R1-P2-OO	10.23	186.90
r4	R1-P2-OO+O₂=R1-P3O4	-8.17	-114.99
r5	R1-P3O4→R1-P4O4	5.82	181.46
r6	R1-P4O4→R1-P5O4	10.51	72.12
r7	R1-P5O4→R1-P6O3H+OH	12.39	65.93
r8	R1-P6O3H→R1-P7O2+OH	11.22	40.56
r9	R1-P7O2→R1-P8	13.28	221.98
r10	R=R2+H	12.39	376.02
r11	R2+O₂=R2-P1-OO	-15.59	-4.77
r12	R2-P1-OO→R2-P2-OO	13.04	214.23
r13	R2-P2-OO+O₂=R2-P3O4	-13.58	-126.50
r14	R2-P3O4→R2-P4O4	8.25	177.35
r15	R2-P4O4→R2-P5O4	8.48	63.67
r16	R2-P5O4→R2-P6O3H+OH	13.84	46.17
r17	R2-P6O3H→R2-P7O2+OH	22.58	28.05
r18	R2-P7O2→R2-P8	11.26	214.78

Fig.6 Temperature dependence of rate constants for reactions starting from α position of decalin with transition states

Fig.7 Rate constants comparison for one-step O2 addition reactions between this work and those calculated by cited literature

Table 2 Results of one-step O2 addition to ethylcyclohexane radicals in the literature

Name of reaction	lg[A/(mol^-1·cm³·s^-1)]	E_a/(kJ·mol^-1)
JetSurF 2.0^[29]	12.06	-6.36
r1^[28]	10.52	-1.09
r2^[28]	10.36	-11.09
r3^[28]	12.28	-4.35
r4^[28]	11.28	-17.62

Table 3 Kinetic parameters of 1,5 H-shift reactions from the literature

Name of reaction	lg(A/s^-1)	E_a/(kJ·mol^-1)
r1^[31]	11.51	100.75
r2^[31]	11.77	97.28
r^[30]	11.42	85.10
r3^[31]	11.78	85.35

Fig.8 Rate constants comparison for 1,5 H-shift reaction and those calculated by the literature

Fig.9 Temperature dependence of equilibrium constants for O2 addition to decalin radicals

参考文献 31

[1]	Hilpert M., Mora B. A., Ni J., Rule A. M., Nachman K. E., Curr. Environ. Health Rep., 2015, 2(4), 412—422
[2]	Ogawa H., Ibuki T., Takayuki M. A., Miyamoto N., Energy Fuels, 2007, 21(3), 1517—1521
[3]	Ranzi E., Energy & Fuels, 2006, 20(3), 1024—1032
[4]	He J. N., Li Y. L., Zhang C. H., Li P., Li X. Y., Acta Phys. Chim. Sinica, 2015, 31(5), 836—842
	(何九宁, 李有亮, 张昌华, 李萍, 李象远. 物理化学学报, 2015, 31(5), 836—842)
[5]	Battin-Leclerc F., Prog. Energ. Combust.Sci., 2008, 34(4), 440—498
[6]	Kyungchan C., Violi A., J. Org. Chem., 2007, 72(9), 3179—85
[7]	Dagaut P., Ristori A., Frassoldati A., Faravelli T., Dayma G., Ranzi E., Proc. Combust. Inst., 2013, 34(1), 289—296
[8]	Zámostný P., Bělohlav Z., Starkbaumová L., Patera J., J. Anal. Appl. Pyrol., 2010, 87(2), 207—216
[9]	Ondruschka B., Zimmermann G., Remmler M., Sedlackova M., Pola J., J. Anal. Appl. Pyrol., 1990, 18(1), 19—32
[10]	Yang Y., Boehman A. L., Combust. Flame, 2010, 157(3), 495—505
[11]	Zeng M., Li Y., Yuan W., Zhou Z., Wang Y., Zhang L., Qi F., Combust. Flame, 2016, 167(5), 228—237
[12]	Zhu Y., Davidson D. F., Hanson R. K., Zhu Y., Davidson D. F., Hanson R. K., Combust. Flame, 2014, 161(2), 371—383
[13]	Zhang W. F., Xian L. Y., Yong K. L., Acta Phys. Chim. Sin., 2016, 32(9), 2216—2222
	(张巍峰, 鲜雷勇, 雍康乐. 物理化学学报, 2016, 32(9), 2216—2222)
[14]	Ranzi E., Frassoldati A., Grana R., Prog. Energ. Combust.Sci., 2012, 38(4), 468—501
[15]	Tan N. X., Wang F., Liu A. K., Guo J. J., Xu J. Q., Li S. H., Li X. Y., The 29th Annual Meeting of the Chinese Chemical Societ., Beijing, 2014
	(谈宁馨, 王繁, 刘爱科, 郭俊江, 徐佳琪, 李树豪, 李象远. 中国化学会第29届学术年会摘要集, 北京, 2014)
[16]	Zhang K., Banyon C., Bugler J., Curran H. J., Rodriguez A., Herbinet O., Battin-Leclerc F., B’Chirc C., Heuferc K. A., Combust. Flame, 2016, 172(10), 116—135
[17]	Rashidi M. J. A., Mehl M., Pitz W. J., Mohamed S., Sarathy S. M., Combust. Flame, 2017, 183, 358—371
[18]	Frisch M. J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Scalmani G., Barone V., Mennucci B., Petersson G. A., Nakatsuji H., Caricato M., Li X., Hratchian H. P., Izmaylov A. F., Bloino J., Zheng G., Sonnenberg J. L., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Nakai H., Vreven T., Montgomery J. A., Peralta J. E., Ogliaro F., Bearpark M., Heyd J. J., Brothers E., Kudin K. N., Staroverov V. N., Kobayashi R., Normand J., Raghavachari K., Rendell A., Burant J. C., Iyengar S. S., Tomasi J., Cossi M., Rega N., Millam J. M., Klene M., Knox J. E., Cross J. B., Bakken V., Adamo C., Jaramillo J., Gomperts R., Stratmann R. E., Yazyev O., Austin A. J., Cammi R., Pomelli C., Ochterski J. W., Martin R. L., Morokuma K., Zakrzewski V. G., Voth G. A., Salvador P., Dannenberg J. J., Dapprich S., Daniels A. D., Farkas O., Foresman J. B., Ortiz J. V., Cioslowski J., Fox D. J., Gaussian 09, Revision A.01, Gaussian Inc., Wallingford CT, 2009
[19]	Becke A. D., J. Chem. Phys., 1998, 98(7), 5648—5652
[20]	Lee C., Yang W., Parr R. G., Phys. Rev. B: Condens. Matter., 1988, 37(2), 785—789
[21]	Gonzalez C., Schlegel H. B., J. Chem. Phys., 1989, 90(4), 2154—2161
[22]	Montgomery J. A., Frisch M. J., Ochterski J. W., Petersson G. A., J. Chem. Phys., 1999, 110(6), 2822—2827
[23]	Altarawneh M. K., Dlugogorski B. Z., Kennedy E. M., Mackie J. C., Combust. Flame, 2013, 160(1), 9—16
[24]	NIST Computational Chemistry Comparison and Benchmark Database, NIST Standard Reference Database Number 101, Release 19, April 2018, Editor, Russell D. Johnson III,
[25]	Mokrushin V. T. W., Zachariah M., Knyazev V., Chem.Rate, Version 1.5.., National Institute of Standards and Technolog., Gaithersburg, MD, 2009
[26]	Zádor J., Taatjes C. A., Fernandes R. X., Prog. Energ. Combust. Sci., 2011, 37(4), 371—421
[27]	Li S. J., Tan N. X., Yao Q., Li Z. R., Li X. Y., Acta Phys. Chim. Sinica, 2015, 31(5), 859—865
	(李尚俊, 谈宁馨, 姚倩, 李泽荣, 李象远. 物理化学学报, 2015, 31(5), 859—865)
[28]	Ning H. B., Gong C. M., Tan N. X., Li Z. R., Li X. Y., Combust. Flame, 2015, 162(11), 4167—4182
[29]	Wang H., Dames E., Sirjean B., Sheen D.A., Tangko R., Violi A., Lai J. Y. W., Egolfopoulos F. N., Davidson D. F., Hanson R. K., Bowman C. T., Law C. K., Tsang W., Cernansky N. P., Miller D. L., Lindstedt R. P.,A High-temperature Chemical Kinetic Model of n-alkane(up to n-dodecane), Cyclohexane, and Methyl-, Ethyl-, n-Propyl and n-Butyl-cyclohexane Oxidation at High Temperatures, JetSurF Version 2.0, September 19, 2010()
[30]	Xing L., Zhang L., Zhang F., Jiang J., Combust. Flame, 2017, 182(8), 216—224
[31]	Miyoshi A., J. Phys. Chem. A, 2011, 115(15), 3301—3325